Conventional design of advanced organic materials that display a variety of desirable properties in a controllable way continues to be one of the great challenges of the contemporary research. Since the initial discovery of organic conducting polymers in the late 1970s, various applications of these materials have been explored due to their exceptional electronic and photonic properties.1-3 
Polythiophenes (PTs) continue to be one of the most versatile and extensively studied conjugated polymer systems due to their exceptional spectroscopic and electronic properties. The straightforward synthesis of PT derivatives generates soluble and processable polymers with a wide range of practical applications, e.g., rechargeable batteries,1 electrochromic devices (ECDs),1 chemical and optical sensors,1 light-emitting diodes (LEDs),4-6 and field-effect transistors (FETs).7 While traditional approaches to synthesize PTs derivatives via electrochemical or oxidative chemical polymerization methods yield polymers with various degrees of regioregularity,3 regioselective synthesis of poly(3-alkylthiophenes) (PATs) that contain almost exclusively head-to-tail (HT) couplings result in improved electrical conductivities and a greater effective conjugation length.
Synthesis of regioregular PATs, first discovered by McCullough et al.8,9 and followed by others,10 results in the formation of defect-free, structurally homogeneous HT-PATs with greatly improved electronic and photonic properties over regiorandom analogues.11,12 Environmental stability can be good. The main difficulty of the original methods lies in the preparation of highly pure 2-bromo-3-alkyl-5-bromomagnesiothiophene.8 This complication has been overcome with the discovery of the Grignard Metathesis (GRIM) method which offers a quick and cost effective technique for the large scale synthesis of high molecular weight, regioregular PATs.13,14 
All of the aforementioned polymerizations are metal-catalyzed cross-coupling reactions.15 The development of efficient catalysts has enormously expanded the scope of these polymerization reactions, where nickel and palladium catalysts with tailored phosphine ligands have been applied. The course of the catalytic reaction has been extensively studied and has been proved to be affected by the ligand structure and the choice of the metal.15 
While the mechanism for the Ni(II) catalyzed cross-coupling reaction (which in some formulations involves a catalytic cycle of three consecutive steps: oxidative addition, transmetalation, and reductive elimination) has been investigated, it continues to remain a subject of investigation.16-26 
The discovery of nickel-catalyzed aryl-aryl bond formations of Grignard reagents with organohalides by Kumada16,17 and Corriu30 has led to a significant development in the synthesis of various types of thiophenes. Consequently, the Kumada reaction has been applied to the synthesis of oligothiophenes and polythiophenes. Despite its use, the mechanism of the nickel-catalyzed cross-coupling polymerization has not been fully understood. Historically, there are three different mechanistic pathways that were independently proposed.16-26 The most plausible mechanistic pathway, which was later extended to cross-coupling polycondensation,31,32 was suggested by Negishi,18,19 Yamamoto,20-22 and Parshall.23 It has been proposed that the reductive elimination and oxidative addition were step-wise processes, which involved formation of a “free” Ni(0) intermediate, with the transmetalation as the rate-determining step. The experimental observations from both McCullough and Grignard metathesis methods invalidated the generally accepted mechanism for the nickel-catalyzed cross-coupling polymerization for the synthesis of regioregular poly(3-alkylthiophenes).
“Living” polymerizations have attracted a great deal of attention due to the fact that they afford polymers with predetermined molecular weights, low polydispersities, specific functionalities and various architectures including block copolymers. See, e.g., Billmeyer, Textbook of Polymer Science, 3rd Ed. John Wiley, 1984, pages 90, 121 and references cited therein; Allcock et al., Contemporary Polymer Chemistry, Prentice-Hall, 1981, pages 72-74, 311-317. These attributes are important for conductive polymers. For example, it is important to have access to regioregular poly(3-alkylthiophenes) and other polythiophenes, including soluble polythiophenes and block copolymers, with controlled molecular weights because the conductivities and other important properties depend on the conjugation length, i.e., on the number of the monomer units incorporated into the polymer. This can result in the ability to tune the electrical conductivity, thereby allowing for the design of materials which are tailor made for specific applications in electronics. One group has recently reported chain growth studies for GRIM metathesis polymerization (Yokoyama et al., Macromolecules, 37, 1169-1171, 2004). However, the monomer employed is not most suitable for commercialization. A need exists, however, to develop alternative controlled polymerization methods and better block copolymers. Commercially useful ingredients and conditions are desired.